WO2005061573A1

WO2005061573A1 - Solvent-free urethane composition

Info

Publication number: WO2005061573A1
Application number: PCT/JP2004/018716
Authority: WO
Inventors: Misao Izumi
Original assignee: Celuster Paint Co., Ltd.
Priority date: 2003-12-19
Filing date: 2004-12-15
Publication date: 2005-07-07

Abstract

Disclosed is a solvent-free composition containing a polyol component (A) and a polyisocyanate component (B) wherein the polyol component (A) is composed of a low molecular weight polyol (A1) having a molecular weight of not more than 350. The viscosity of the low molecular weight polyol (A1) may be 500 mPa·s or less at 25˚C, and the low molecular weight polyol (A1) may be, for example, a C2-6 alkylene glycol. Alternatively, the polyol component (A) may be composed of the low molecular weight polyol (A1) as a diluent and a polymer polyol (A2). The polyisocyanate component (B) may be a modified body or derivative of a polyisocyanate (such as a polymer of a diisocyanate). The solvent-free composition may further contain an epoxidized compound (C) which may optionally contain a hydroxyl group (such as an aliphatic diol glycidyl ether or an aliphatic polyol glycidyl ether having a hydroxyl group). This solvent-free composition causes only small damage to the environment, and has excellent coating properties and a high working efficiency.

Description

Specification

Solvent-free urethane composition

Technical field

The present invention relates to a solvent-free urethane composition excellent in physical properties and workability of a coating film with a small environmental load, and a use thereof.

Background art

[0002] Polyurethane resins have high abrasion resistance, chemical resistance, flexibility, etc., and are widely used as coating compositions or paints for buildings, building members, various vehicles, machinery and equipment, plastic products, textile products, and the like. It's being used. On the other hand, in the coatings field in recent years, regulations on the emission of VO c (volatile organic compounds) into the atmosphere have become stricter, and urethane coatings will replace solvent-based coatings that have been widely used in the past. Paints are desired. Water-based paints and powder paints have been developed as alternatives to solvent-based paints. However, the water-based paint contains an emulsifier and a dispersant, and the resin is hydrophilized. Therefore, it takes a long time to dry the paint film if the water resistance of the paint film is not sufficient. In the case of powder coatings, thick coating is difficult, and the adhesion of the coating film is low. Therefore, solventless urethane paints have been developed as non-solvent paints to remedy these drawbacks.

[0003] For example, Japanese Patent Application Laid-Open No. 10-292150 (Patent Document 1) discloses a polyurethane paint that can be applied without a solvent, and can form a coating film having excellent water resistance, salt water shielding properties, and followability. As the coating material, (a) a polyhydric alcohol having a dimer diol content of 50 to 100% by weight and a viscosity at 25 ° C of 2000 mPa's (cps) or less, and (b) a viscosity at 25 ° C of 200 to 2000 mPa Disclosed are two-part polyurethane coatings comprising 's aliphatic or cycloaliphatic isocyanates. In the examples of this document, (a) a mixture of dimer diol, 3-methylpentanediol, and a force having a viscosity of 1200 mPa · s is used as the polyhydric alcohol. However, this urethane paint has low coatability and low hardness of the coating film

[0004] Further, Japanese Patent Application Laid-Open No. 2000-136226 (Patent Document 2) discloses that dimer diol contains alkylene oxide as a coating material capable of forming a coating film having excellent coating properties and water resistance even without solvent. A low-viscosity polyol mixture containing 50% by weight or more of the added diol compound and having a viscosity at 25 ° C of 2000 mPa's or less, and a polyisocyanate having a viscosity at 25 ° C of 2000 mPa's or less 2 Liquid polyurethane coatings are disclosed. This document describes that dimer diol is an aliphatic diol having 36 carbon atoms obtained by hydrogenating dimer monoacid obtained by dimerizing unsaturated fatty acid having 18 carbon atoms. In the examples, an ethylene oxide adduct of a dimer diol having a number average molecular weight of about 800 and 1030 is used. However, even with this urethane paint, the work efficiency and the hardness of the coating film are low, and the transparency and smoothness are reduced particularly under high humidity.

Further, JP-A-9-1221627 (Patent Document 3) discloses a polyol composed of a polyol having two or more hydroxyl groups per molecule and an acrylic resin having a hydroxyl group and having a glass transition temperature of 0 to 90 ° C. A solvent-free urethane coating composition for concrete coating formwork plywood, in which a modified acrylic resin contains a polyisocyanate conjugate, has been disclosed. This document describes that a polyol-modified acrylic resin is prepared by radical copolymerization of an unsaturated monomer constituting the acrylic resin component in the presence of a polyol component. Use polyether polyols. However, even with this urethane coating composition, the coating properties and handleability are high due to high viscosity.

Patent Document 1: JP-A-10-292150 (Claim 1, paragraph number [0014] [0015]) Patent Document 2: JP-A-2000-136226 (Claims 1 and 3, paragraph number [0006] [0013] ] [0014])

Patent Document 3: Japanese Patent Application Laid-Open No. 9-221627 (Claim 1, Paragraph No. [0024] [0032])

Problems to be solved by the invention

[0006] Accordingly, an object of the present invention is to provide a urethane-based composition having a small coating load such as hardness and abrasion resistance that has a small load on the environment and uses thereof.

[0007] Another object of the present invention is to provide a solventless urethane-based composition capable of forming a coating film having a smooth surface, capable of suppressing a decrease in thickness and turbidity due to foaming and drying even if the coating film has a large thickness. Its purpose is to provide its use.

[0008] Still another object of the present invention is to provide a non-solvent type having a small load on the environment and high workability. An object of the present invention is to provide a urethane resin composition and its use.

[0009] Another object of the present invention is to provide a solventless urethane-based resin composition that can achieve both coating properties such as hardness / abrasion resistance and coatability such as adhesion to a substrate and applicability. It is here.

[0010] Still another object of the present invention is to provide a coating film having excellent appearance (design, high gloss, coloring, etc.), a good balance between pot life and drying (or curability), and various resistances ( An object of the present invention is to provide a solventless urethane composition excellent in non-staining property, fire resistance, water resistance, weather resistance, chemical resistance, etc.) and its use.

Means for solving the problem

The present inventors have conducted intensive studies in order to achieve the above-mentioned object. As a result, in a solvent-free urethane composition such as a paint or an adhesive, a low-molecular-weight polyol component and a polyisocyanate (for example, an isocyanurate ring are used). When combined with a polyisocyanate, which has a low environmental load, the coating properties such as hardness and abrasion resistance increase, and the polymer polyol is added and the low-molecular-weight polyol is diluted with a diluent. As a result, the present inventors have found that the load on the environment is small and the workability is high, and the present invention has been completed.

That is, the solvent-free composition of the present invention is a composition composed of the polyol component (A) and the polyisocyanate component (B), and at least the polyol component (A) has a molecular weight of 350 or less. Low molecular polyol (A1). The viscosity of the low-molecular polyol (A1) may be 500 mPa's or less at 25 ° C. The low-molecular-weight polyol (A1) may be, for example, C alkylene glycol. The molecular weight of the polyisocyanate component (B) may be about 150 to 3000, and the molecular weight of the polyisocyanate component (B) may be larger than the molecular weight of the low molecular polyol (A1).

[0013] The polyol component (A) may be composed of a low molecular polyol (A1) as a diluent and a polymer polyol (A2). The proportion of the low-molecular polyol (A1) may be, for example, about 5 to 100 parts by weight (particularly, 7 to 80 parts by weight) based on 100 parts by weight of the polymer polyol (A2). The polymer polyol (A2) may be a polyether polyol, a polyester polyol, a polycarbonate polyol, an acrylic polymer polyol, or the like. [0014] The polyisocyanate component (B) may be a derivative or a modified product of polyisocyanate (for example, a diisocyanate multimer). The ratio of the isocyanate group of the polyisocyanate component may be about 0.5 to 1.5 monoles (particularly 0.7 to 1.3 moles) per mole of the hydroxyl group of the polyol component. Ray.

[0015] The composition further comprises a compound (C) having an epoxy group, for example, a compound having a viscosity of about 200 mPa's at 25 ° C and having a plurality of glycidyl groups (aliphatic diene). Diglycidyl ether, etc.). The compound having an epoxy group may further have a hydroxyl group. Addition of an epoxy group-containing compound can suppress white turbidity and foaming of the coating film. The ratio of the epoxy group-containing compound (C) is about 100 parts by weight (particularly 580 parts by weight) based on 100 parts by weight of the total of the polyol component (A) and the polyisocyanate component (B). It may be. Such a solventless composition is suitable for a coating agent, an adhesive or the like.

[0016] The present invention also includes a method of coating a surface of a substrate (such as a substrate having a non-flat surface) with the composition to form a coating film.

[0017] In the present specification, the term "solvent-free composition" refers only to a composition containing no solvent at all and a composition containing substantially no solvent (low VOC composition). It is used in the sense that also includes.

The invention's effect

In the present invention, since a low molecular weight polyol component and a polyisocyanate component are combined, it is possible to improve coating film properties such as hardness and abrasion resistance, which have a small load on the environment. In addition, by thick coating, even if the thickness of the coating film is large, it is possible to suppress the reduction in thickness and cloudiness due to foaming and drying, and to form a coating film having a smooth surface.

Further, when a low molecular polyol is used as a diluent, even a solventless (low VOC) urethane-based resin composition in which a polymer polyol and a polyisocyanate component are combined can reduce the viscosity and improve the paintability and paintability. Workability can be improved, and the burden on the environment can be reduced. In addition, by adjusting the types and quantitative ratios of low molecular polyols and polymer polyols as diluents, coating properties such as hardness / abrasion resistance and coating properties such as adhesion to substrates and coatability are improved. Can be compatible. [0020] Furthermore, the coating film is excellent in appearance (design, high gloss, coloring, etc.), and has a good balance between pot life and drying properties, so that workability is improved. In addition, since a reactor is unnecessary, it is economically advantageous. Furthermore, it is excellent in non-staining, fire resistance, water resistance, weather resistance and chemical resistance.

Detailed description of the invention

[0021] The solvent-free composition of the present invention comprises a polyol component (A) and a polyisocyanate component (B). This composition may further contain a compound having an epoxy group (epoxy group-containing compound) (C). Since the composition of the present invention is a solventless type, it has low VOC generation and flammability.

[0022] [Polyol component (A)]

In the present invention, the polyol component (A) is composed of at least a low molecular polyol (A1). The molecular weight of the low-molecular polyol (A1) is, for example, 350 or less (for example, 50-330), preferably 62-300 (62-200 for f-line), and more preferably 76-150 (particularly 76-120). It is about.

Examples of the low-molecular polyol (A1) include, for example, aliphatic diols (ethylene glycol, 1, 2_ or 1, 3_ propylene glycol, 1, 4_, 1, 3_ or 1, 2, butanediol, 2 — Methinole, 1,3_propanediol, neopentyl glycol, 1,5_pentanediol, 3-methinole-1,5_pentanediol, 1,6-hexanediol, 1,7_heptanediol, 2, 2,4_trimethylpentane-1,3-diol, 1,8-octanediol, 2-methylone-1,8_octanediol, 1,10-decanediol, 1,11-decanediol, 1, C-alkanediol such as 12-decanediol), (poly) ether diol

1-12

(Di- to tri-C alkylene ether glycols such as diethylene glycolone, triethylene glycolone, dipropylene glycolone, propylene glycol, ditrimethylene ether glycol, ditetramethylene ether glycol, etc.), aliphatic polyols (glycerol)

2-4

Of trimethylolpropane, trimethylolethane, pentaerythritol, etc.

3-12 Aliphatic polyols, etc.), Alicyclic diols (Cycloalkanediols such as cyclohexanediol, cyclohexanedimethanol, hydrogenated bisphenol A, C alkylene oxide adducts of this cycloalkanediol, etc.), and aromatics Diol (xylylene glycol And a C alkylene oxide adduct of bisphenol A). These polyol components can be used alone or in combination of two or more.

[0024] Among these low-molecular polyols, aliphatic diols (eg, C alkylene glycols such as propylene glycol, butanediol, neopentyl glycol, and hexanediol) and aliphatic polyols (eg, trimethylolethane, trimethylol) (Propane etc.), (poly) oxy C alkylene glycol (dioxy such as dipropylene glycol)

C alkylene glycol), especially C alkylene glycol such as butanediol is preferred.

[0025] Further, a polyol having a branched chain, for example, propylene glycol, dipropylene glycol, or the like may show high solubility in a polymer polyol. Therefore, it is effective when the low molecular polyol (A1) is used in combination with the polymer polyol.

[0026] The low-molecular polyol (A1) is usually a liquid at room temperature (15 to 25 ° C). Note that even a compound that is solid at room temperature can be used as a liquid polyol by combining it with another polyol. The viscosity of the low-molecular polyol (A1) at 25 ° C. is 500 mPa's (cps) or less (for example, 1 to 500 mPa's), preferably 3 to 300 mPa's (for example, 3 to 200 mPa's). And more preferably about 5 to 100 mPa's (particularly about 10 to 100 mPa's).

In the present invention, by using such a low-molecular polyol (A1) as the polyol component (A), a coating film having high hardness and high abrasion resistance can be formed, and even if the film is thickly coated, The thickness reduction (thinning) due to foaming and drying can be suppressed. Therefore, generation of cracks and the like in the coating film can be suppressed, and a coating film having a smooth surface is formed. Further, even if the surface of the material to be coated (base material) is a rough surface having fine cracks, irregularities or steps, a smooth and strong coating film can be formed irrespective of the surface shape of the base material. For example, even when the base material has joints and the like, a coating film having a smooth surface can be formed by a single application. In addition, it has excellent appearance properties, stain resistance (dirt collection resistance), and fire resistance of the coating film surface.

Further, in the present invention, such a low-molecular polyol (A1) may be used as a first polyol and combined with a polymer polyol (A2) as a second polyol. Combined like this In addition, by using low-molecular-weight polyol (Al) as a part of the polyol component, the low-molecular-weight polyol acts as a solvent (reactive diluent) even though the VOC content is extremely small, The viscosity can be reduced, and the workability and paintability can be improved. In addition, by increasing the proportion of low-molecular polyol, it is possible to form a coating film with high hardness and abrasion resistance, and to suppress the reduction in thickness (thinning) due to foaming and drying of the coating film even when applied thickly. it can. Therefore, generation of cracks and the like in the coating film can be suppressed, and a coating film having a smooth surface can be formed. Furthermore, it has excellent appearance characteristics, stain resistance (dirt collection resistance), and fire resistance of the coating film surface.

[0029] Examples of the polymer polyol (A2) include a polyether polyol, a polyester polyol, a polycarbonate polyol, and an acrylic polymer polyol. These polymer polyols can be used alone or in combination of two or more.

Examples of the polyether polyol include, for example, homo- or copolymers of alkylene oxides

[Poly (C alkylene glycol) such as polyethylene glycol, polypropylene glycol, polytrimethylene ether glycol, polytetramethylene ether glycol],

2-4

An alkylene oxide adduct of sphenanol A or hydrogenated bisphenol A may be mentioned. These polyether polyols can be used alone or in combination of two or more.

Examples of the polyester polyol include, for example, a reaction product of the low-molecular polyol (A1) with dicarboxylic acid or a reactive derivative thereof (lower alkyl ester, acid anhydride), and ratatone (buty ratatone, valerolatatone) C lacto, such as force pro rataton, lau mouth rataton

3-12) and the like (ring-opened polymers).

[0032] Examples of the dicarboxylic acid include aliphatic dicarboxylic acids (for example, aliphatic C aliphatic dicarboxylic acids such as adipic acid, suberic acid, azelaic acid, sebacic acid and dodecanedicarboxylic acid).

4-14

Examples thereof include an alicyclic dicarboxylic acid (eg, tetrahydrophthalic acid, tetrahydroisophthalic acid, tetrahydroterephthalic acid, etc.) and an aromatic dicarboxylic acid (eg, phthalic acid, terephthalic acid, isophthalic acid, etc.). . These dicarboxylic acids can be used alone or in combination of two or more. Dicarboxylic acid may be used if necessary You may use together with polyvalent carboxylic acids, such as romellitic acid.

[0033] These polyester polyols can be used alone or in combination of two or more.

[0034] Examples of the polycarbonate polyol include, for example, the low-molecular polyol (A1) and a dialkyl carbonate (such as di C alkyl carbonate such as dimethyl carbonate).

1-4

ゃ Caryl carbonate (such as diphenyl carbonate)

6-12

And the like. These polycarbonate polyols can be used alone or in combination of two or more.

The acrylic polymer polyol may be an acrylic polymer polyol in which a hydroxyl group is introduced by modifying an acrylic polymer, but usually, a (meth) acrylic monomer having a hydroxy group Is a (meth) acrylic polymer in which a hydroxyl group has been introduced by polymerization of a polymer.

[0036] Examples of the (meth) acrylic monomer having a hydroxy group include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-hydroxy (meth) acrylate. Hydroxy C alkyl esters of (meth) acrylate such as xyloxypropyl, 4-hydroxybutyl (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glyco

2-4

Poly (C) alkylene glycol (meth) acrylate such as polyester (meth) acrylate

2-4

I can do it. These hydroxyl group-containing (meth) acrylic monomers can be used alone or in combination of two or more. Of these hydroxyl group-containing (meth) acrylic monomers, hydroxy C alkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate are preferred. Masire,

2-4

[0037] The (meth) acrylic monomer having a hydroxy group may be copolymerized with another copolymerizable monomer. Other copolymerizable monomers include, for example, (meth) acrylic acid, (meth) atalinoleate [methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate

C-alkyl (meth) acrylates, such as hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate

1-20

No., phenyl (meth) acrylate, benzyl (meth) acrylate, glycidyl (meth) acrylate], butyl cyanide monomers such as acrylonitrile, and Α-C olefins such as propylene), aromatic vinyl (styrene, vinyl toluene,

2-10

α-methylstyrene, etc.) and carboxylic acid vinyl esters (eg, Biel acetate). Other copolymerizable monomers can be used alone or in combination of two or more. Among these other copolymerizable monomers, (meth) atalylic esters such as alkyl (meth) acrylate, glycidyl (meth) acrylate, and aromatic vinyl such as styrene, particularly (meth) C alkyl (meth) acrylates such as methyl acrylate and butyl (meth) acrylate

1-4 steles are preferred.

[0038] The ratio (weight ratio) of the hydroxyl group-containing acrylic monomer to the other copolymerizable monomer is

Can be appropriately selected according to the hydroxyl value of the acrylic polymer polyol. For example, the former Ζ the latter = 100 / 0—1 / 99, preferably <80 / 20—3,97, and more preferably <50,50.

About 5/95 (especially 30-70 10/90).

[0039] The acrylic polymer polyol may be modified with fluorine depending on the use. The method of modification with fluorine is not particularly limited, but is usually a method of preparing a modified fluorine copolymer by polymerizing a fluorine-containing butyl monomer as a copolymerizable monomer. Examples of the fluorine-containing biel monomer include, for example, fluorine-containing C olefin monomers such as tetrafluoroethylene, chlorofluoroethylene, vinylidene fluoride, dichlorodifluoroethylene, butyl fluoride, and hexafluoropropylene; Trifluorome

2-6

Perfluoro c alkyl vinyl ethers such as norevier ethers

1-4

. These fluorine-containing vinyl monomers can be used alone or in combination of two or more. Of these monomers, fluorine-containing olefins such as tetrafluoroethylene, vinylidene fluoride, vinyl fluoride, and hexafluoropropylene are preferred.

2-4

Les ,.

[0040] The proportion of the fluorine-containing bull-based monomer is, for example, about 180 to 80% by weight, preferably about 360% by weight, and more preferably about 550% by weight (particularly about 1040% by weight) in all the monomers. is there.

[0041] Among these polymer polyols, acryl-based polymer polyols are preferred because they can easily impart various functions depending on the application.

[0042] These polymer polyols have a functional group for improving weather resistance such as light resistance. May be provided. For example, an acrylic polymer polyol is an acrylic monomer having a light-stable group [eg, 4_ (meth) atalyloyloxy 2,2,6,6-tetramethylpiperidine, 4_ (meth) atalyloyloxy 1 (Meth) atalyloyloxy-alkylpiperidines, such as 4,2,2,6,6_pentamethylpiperidine, and acrylic monomers having a 4_ (meth) atalyloylamino-2,2,6 UV-absorbing group Copolymers with 2- (2'-hydroxy-5 '-(meth) atali ester xicetyl phenol)-2H-benzotriazole and other hydroxy- (meth) atali ester xylkylbenzoylbenzotriazoles It may be. The ratio of the monomer having a functional group is, for example, about 0.1 to 30% by weight, preferably about 0.5 to 20% by weight, and more preferably about 110 to 10% by weight, based on all monomers. is there. Thus, by introducing an ultraviolet absorbing group into the polymer polyol, bleed out can be suppressed and the light resistance effect can be maintained for a long period of time, as compared with the case where an ultraviolet absorbing agent is added.

The hydroxyl value of the polymer polyol is, for example, about 10 to 400 KOH mg / g, preferably about 20 to 300 KOH mg / g, and more preferably about 30 to 250 KOtimg / g (about 50 to 200 KOti mg / g). Yes, usually about 20-200K〇Hmg / g.

[0044] The ratio of the low-molecular polyol (A1) to the polymer polyol (A2) may be, for example, 100 parts by weight of the polymer polyol (A2) based on the viscosity, coating properties, coating properties, and the like. Polyol (Al) l—Can be selected from the range of about 100 parts by weight, for example, 5 to 100 parts by weight, preferably 7 to 80 parts by weight, more preferably 10 to 75 parts by weight, 10 to 60 parts by weight, 15 to 50 parts by weight. It is about parts by weight. The proportion of the low-molecular polyol (A1) may be, for example, about 3-80 parts by weight, preferably about 550 parts by weight (particularly, 1030 parts by weight) based on 100 parts by weight of the polymer polyol (A2).

[Polyisocyanate component (B)]

Examples of the polyisocyanate component (B) include aliphatic polyisocyanates [propylene samethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMDI), and lysine diisocyanate (LDI). ) And 1, 6, 11_ Aliphatic triisocyanates such as cantriisocyanate methyl octane, 1,3,6-hexamethylene triisocyanate], alicyclic polyisocyanates [cyclohexane 1,4-diisocyanate, isophorone diisonate Alicyclic diisocyanates such as cyanate (IPDI), hydrogenated xylylene diisocyanate, hydrogenated bis (isocyanatophenyl) methane, and alicyclic triisocyanates such as bicycloheptane triisocyanate], Aromatic polyisocyanate [phenylene diisocyanate, tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), tetramethyl xylylene diisocyanate (TMXDI), naphthalene diisocyanate (NDI), bis (isocyanatophenyl) methane (MDI), toluidine diisocyanate (TODI), 1,3_bis (I Cyanatophenyl) etc. aromatic Jiisoshianeto such as propane], and others.

[0046] These polyisocyanate components include multimers (dimers, trimers, tetramers, and the like), adducts, and modified products (such as a modified buret, a modified allohanate, and a modified urea). Or a urethane oligomer having a plurality of isocyanate groups.

[0047] In addition, these polyisocyanate components are usually hydrophobic polyisocyanates, and include hydrophilic groups [for example, nonionic groups (hydroxyl group, (poly) oxyethylene group, alkylphenyl (poly)). Hydrophilic polyisocyanate into which an anionic group (such as a carboxyl group or a sulfonic acid group) or a cationic group (such as a tertiary amino group) has been introduced. Hydrophilic polyisocyanates are available from Nippon Polyurethane Industry Co., Ltd. under the trade names "Aquanate 100 (AQ-100)", "AQ-110", "AQ-120", "AQ-200", Available as "AQ_210".

[0048] Further, these polyisocyanate components are block-type polyisomers protected by a protecting group such as isocyanate-based ratatams (such as proprolactam) and oximes (such as methylethylketoxime and acetoxime). It may be a cyanate.

[0049] These polyisocyanate components can be used alone or in combination of two or more.

[0050] Among these polyisocyanate components, a modified or derivative of polyisocyanate, a urethane oligomer having a plurality of isocyanate groups, and the like are preferable. Among them, from the viewpoint of weather resistance, non-yellowing polyisocyanate (for example, aliphatic polyisocyanate and alicyclic polyisocyanate). Modified products or derivatives of polyisocyanates such as isocyanates), particularly aliphatic isocyanates or derivatives thereof (for example, hexamethylene diisocyanate or trimers thereof) are preferred.

[0051] Examples of modified polyisocyanates or derivatives include polyisocyanates (such as aliphatic polyisocyanates such as hexamethylene diisocyanate) and polyhydric alcohols (trimethylolpropane and the like). Adduct with pentaerythritol), a burette of the polyisocyanate, a multimer of the polyisocyanate, and the like can be preferably used. From the viewpoint of coating properties such as appearance and strength, the polymer has an isocyanurate ring such as a polyisocyanate (for example, aliphatic polyisocyanate) multimer (for example, hexamethylene diisocyanate trimer). Polyisocyanates and the like are particularly preferred. Such polyisocyanates can be obtained, for example, as trade names “Takenate D_170N”, “Takenate D-170HN”, and “Takenate D-177N” from Mitsui Takeda Chemiconore Co., Ltd., and from Nippon Polyurethane Industry Co., Ltd. Available under the trade names "Coronate R301" and "Coronate R303".

[0052] The molecular weight of the polyisocyanate component (B) can be selected from the range of about 150 to 3000, preferably 250 to 2000, more preferably 300 to 1500 (300 to 1000, especially 400 to 700 for f-line). ) Degree. Further, the molecular weight of the polyisocyanate component (B) is preferably larger than the molecular weight of the low molecular weight polyol (A1). For example, the difference in molecular weight between the two is, for example, 50-1000, preferably 100 —800, more preferably about 250-750.

The viscosity (viscosity at 25 ° C.) of the polyisocyanate component (B) is about 100 to 5000 mPa's depending on the viscosity of the polyol component (A) and the epoxy group-containing compound (C) described below. A range force can also be selected, for example, on the order of 150-3000 mPa's, preferably 200-2000 mPa's, more preferably on the order of 300-1500 mPa's (particularly 300 lOOmPa's). Further, the viscosity of the polyisocyanate component is also preferably larger than the viscosity of the polyol component. For example, the difference in viscosity between the two is, for example, about 100 2000 mPa * s, preferably about 300 1000 mPa's. You may.

[0054] Further, when the polymer polyol (A2) is added, for example, about 200 to 3000 mPa-s, preferably about 250 to 2500 mPa's, more preferably about 500 to 2500 mPa's. Oh good.

[0055] The ratio of the polyol component (A) to the polyisocyanate component (B) is such that the hydroxyl group of the polyol component (A) is substantially equivalent to the isocyanate group of the polyisocyanate component (B). Degree, for example, the ratio of the isocyanate group to the hydroxyl group relative to 1 mole of the hydroxyl group is 0.5-1.5 monole, preferably 0.7-1.3 monole, more preferably 0.8-1.2 monole. Even though there is. The weight ratio of the two components can be selected from a range of about 5,000 parts by weight of the polyisocyanate component (B) to 100 parts by weight of the polyol component (A). The polyisocyanate component (B) may be 200 to 3000 parts by weight, preferably 300 to 2000 parts by weight, and more preferably about 500 to 1500 parts by weight.

[Compound (C) Having Epoxy Group]

The urethane-based resin composition of the present invention may contain a compound having an epoxy group (epoxy group-containing compound) (C). When an epoxy group-containing compound is used, freezing of the polyol component can be suppressed when a polyol component having a low freezing point (for example, a C alkanediol such as butanediol) is used. When an epoxy group-containing compound is used, the pot life is prolonged, and the workability is improved. In addition, by using the epoxy group-containing compound, it is possible to prevent the coating film from becoming cloudy or foaming under high humidity, and to reduce the transparency and the smoothness. Furthermore, thick coating can suppress the reduction in thickness and cloudiness due to foaming and drying even when the thickness of the coating film is large, and can form a coating film having a smooth surface. However, since the light resistance of the coating film tends to be slightly reduced, it is preferable to use it in combination with an ultraviolet-absorbing polymer polyol or an ultraviolet absorber in applications requiring light resistance.

The compound having an epoxy group includes a compound having a glycidyl group, an alicyclic epoxy compound, and the like, and a compound having a glycidinole group is usually used. Examples of the compound having a glycidyl group include a glycidyl ether compound, a glycidyl ester compound, and a glycidinoleamine compound. These epoxy group-containing compounds can be used alone or in combination of two or more.

[0058] Examples of the glycidyl ether-based compound include aliphatic diol dalicidylate Nole (for example, ethylene glycol glycidyl ether, propylene glycol glycidyl ether, butanediol dalicidyl ether, neopentyl glycol glycidyl ether, 1,5-pentanediol daricidyl ether, 1,6-hexanediol dalicidyl ether, 1,7-heptanediol daricidyl ether, 2,2,4-trimethylpentane-1,3-dioldaricidyl ether, 1,8-octanediol daricidyl ether, 1,10-decanediol daricidyl ether, etc. C alkanediol mono or

2-20

Is diglycidyl ether), polyether diol daricidyl ether (diethylene glycol corn glycidinoleate ethere, triethylene glycol corn glycidinoleate ethere, dipropylene glycol glycidyl ether, etc.

2-4

C fats such as glycidyl ethers), aliphatic polyols daricidyl ethers (for example, glycerin ricidinoleate ether, trimethylonolepropane glycidinoleatenole, trimethylonoleetane ricidyl ether, pentaerythritol glycidyl ether, etc.) Tribe polio

3-12

Mono- to tetraglycidyl ethers), alicyclic diol dalicidyl ethers (eg, cyclohexanediol dalicidyl ether, cyclohexane dimethanol glycidyl ether, etc.), aromatic diol dalicidyl ethers (eg, resorcining ricidyl ether) And the like, and heterocyclic polyol daricidyl ether [eg, glycidyl ether of (iso) cyanuric acid]. These glycidyl ether compounds can be used alone or in combination of two or more.

[0059] Examples of the glycidinole ester-based compound include aliphatic saturated carboxylic acid glycidyl esters (glycidyl C-aliphatic carboxylate such as glycidyl acetate, glycidyl propionate, glycidyl butyrate, daricidyl diprolate, and glycidinole laurate). , Aliphatic

4-20

Glycidyl carboxylate [glycidinol (meth) acrylate], glycidyl dicarboxylate (glycidyl succinate, glycidyl glutarate, glycidinole adipate, glycidinole sebacate, etc.) Or diglycidinole

5-20

Esters and the like). These glycidyl ester compounds can be used alone or in combination of two or more.

[0060] Examples of the glycidinoleamine-based compound include tetraglycidyldiaminodiphenylmethane, triglycidylaminophenol, diglycidylazirin, diglycidyltoluidine, and tetramethyldiamine. Aminomethylcyclohexane and the like. These glycidylamine compounds can be used alone or in combination of two or more.

[0061] Among these epoxy group-containing compounds, aliphatic glycidyl ether compounds having a plurality of glycidinole groups, for example, neopentyl glycol diglycidyl ether,

C-alkanediol diglycidyl ethers such as 6-hexanediol diglycidyl ether and (poly) C alkylene glycol diglycidyl ether are preferred. Further, the epoxy group-containing compound may have a hydroxy group in order to improve the appearance and physical properties of the coating film. Examples of the epoxy group-containing compound having a hydroxyl group (or a compound having a plurality of glycidyl groups and hydroxyl groups) include, for example, glycerin diglycidinoleatene, trimethylonolepropane diglycidinoleatene, and trimethylonoleethane diglycidyl. Aliphatic polyols such as ether, pentaerythritol di or triglycidyl ether, and the like are preferred. Further, an epoxy group-containing compound having no hydroxyl group and an epoxy group-containing compound having a hydroxyl group may be used in combination.

[0062] The epoxy equivalent of the epoxy group-containing compound is not particularly limited.

00 g / eq, preferably 70-500 g / eq, more preferably 100-300 g / eq (particularly 10

0-250g / eq).

[0063] The molecular weight of the epoxy group-containing compound can be selected from the range of about 110 to 1000, preferably about 120 to 700, and more preferably about 150 to 500 (particularly about 150 to 300).

[0064] The viscosity of the epoxy group-containing compound is preferably low from the viewpoint of coating workability, for example, 200 mPa's or less at 25 ° C (eg, 200 mPa's), preferably 1 lOOmPa's (for example, 2-100 mPa's), more preferably 3-50 mPa's (particularly 5-100 mPa's)

30mPa's).

[0065] The proportion of the epoxy group-containing compound (C) is, for example, 1 to 100 parts by weight, preferably 58 to 100 parts by weight of the total of the polyol component (A) and the polyisocyanate component (B).

0 parts by weight, more preferably about 10-50 parts by weight.

When the polymer polyol component (A2) is added, the proportion of the epoxy group-containing compound (C) May be, for example, about 3 to 80 parts by weight, preferably about 5 to 50 parts by weight, based on 100 parts by weight of the total of the polyol component (A) and the polyisocyanate component (B).

[0067] In the solvent-free composition of the present invention, a urethanization catalyst may be added to promote the urethanization reaction. Examples of urethanization catalysts include conventional organometallic catalysts such as dibutyltin dilaurate (DBTDL), dibutynoletin marker peptide, dioctinoretin mercaptide, dibutyltin dimaleate, dibutyltin dimalate, and dibutyltin thiocarboxylate. A system catalyst can be used. These urethane catalysts can be used alone or in combination of two or more. The proportion of the urethanization catalyst can be used within a range of 5 parts by weight or less (0.5 part by weight) based on 100 parts by weight of the total of the polyol component (A) and the polyisocyanate component (B). — 1 part by weight, preferably about 0.005 to 0.1 part by weight, and more preferably about 0.005 0.05 part by weight. If the proportion of the urethane-forming catalyst is too large, bubbles are generated and the curing time is shortened.

[0068] The solvent-free composition of the present invention further includes a conventional pigment component such as an inorganic pigment (white pigment such as titanium oxide, yellow pigment such as titanium yellow, red pigment such as iron oxide red, chromium). Green pigments such as green, blue pigments such as cobalt blue, black pigments such as carbon black, etc.), organic colorants (azo dyes, phthalocyanine dyes, lake dyes, etc.), extender pigments (calcium carbonate, Barium sulfate, aluminum hydroxide, aluminum hydroxide, talc, alumina, bentonite, magnesium oxide, etc., gloss pigments (metal foil such as stainless flake, metal powder such as aluminum, zinc, copper, glass powder, glass sphere, glass) Flakes, glass fibers, graphite, etc.). Further, the pigment component may be a water-proof pigment (for example, an aluminum-containing compound such as aluminum powder, zinc powder, and condensed aluminum phosphate). These pigment components can be used alone or in combination of two or more.

[0069] The proportion of these pigment components can be adjusted according to the application. For example, about 1 to 1000 parts by weight of the total of 100 parts by weight of the polyol component and the polyisocyanate component is used. It can be selected from a range, for example, about 3 to 500 parts by weight, preferably about 5 to 300 parts by weight, and more preferably about 10 to 100 parts by weight.

[0070] The solvent-free composition of the present invention may further contain a conventional additive such as a filler, Oral adhesives, viscosity modifiers, dispersants, wetting agents, plasticizers, defoaming agents, cross-linking agents, cutting agents (silane coupling agents, titanium coupling agents, etc.), curing accelerators, leveling agents , Lubricants, flame retardants, stabilizers (antioxidants, ultraviolet absorbers, heat stabilizers), antistatic agents, etc. may be added. In particular, when organic powdery granular waste such as wood flour, cork flour, and plastic flour is used as the filler, the heat retention and cushioning properties can be improved and the resources can be effectively used. These additives can be used alone or in combination of two or more.

[0071] In particular, this is a composition obtained by adding the polymer polyol component (A2) and is used for applications requiring light resistance, and the polymer polyol component (A2) has an ultraviolet absorbing group. If not, a benzotriazole UV absorber [2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl Hydroxyl and alkyl groups such as 5-benzotriazoles substituted with arylarylbenzotriazoles, etc.], and cyanoacrylate ultraviolet absorbers [2-ethylhexyl1-2-cyano-1,3,3 ' —Diphenyl atalylate, ethyl 2-—cyano-1,3,3 ′ —diphenyl atalylate and other cyano-containing diaryl acrylates, etc.], benzophenone-based UV absorbers [2,4-dihydroxyben Hydroxy and / or alkoxy-substituted benzophenones, such as phenone, 2-hydroxy-4-monoethoxybenzophenone, and 2-hydroxy-4-methoxybenzophenone], salicylic acid ultraviolet absorbers (phenyl salicylate, p_t_butylphenyl salicylate, p-octylphenyl salicylate, etc.] and the like. These UV absorbers can be used alone or in combination of two or more.

[0072] The method for preparing the solvent-free composition of the present invention is not particularly limited, and it can be prepared by a conventional method of mixing the components. In the preparation of the composition, each component may be added at once, or may be added in any order. For example, the components of the polyol component (A) and the polyisocyanate component (B) or any of the components may be added before painting without adding the components at once.

Further, when adding the polymer polyol (A2), the polyol (A) may be prepared by separately preparing the low-molecular-weight polyol (A1) and the polymer polyol (A2), Low A mixture of both may be prepared by polymerizing the monomers constituting the polymer polyol (A2) in the molecular polyol (Al). When the polymer polyol (A2) is commercially available as a solution containing an organic solvent, a low molecular polyol (A1) having a boiling point higher than that of the organic solvent was added to the organic solvent solution of the polymer polyol. Thereafter, the organic solvent is removed by heating (preferably heating under reduced pressure) at a temperature not lower than the boiling point of the organic solvent and not higher than the boiling point of the low-molecular polyol (A1). And a mixture of both may be prepared.

[0074] The solvent-free composition of the present invention can be used for various uses such as an adhesive and a coating agent (paint). For example, when the polyol component (A) is composed of a low molecular polyol, it is suitable for use as a coating agent (paint).

As a method for applying the solvent-free composition of the present invention to a substrate such as an object to be coated or an object to be adhered, a conventional method such as brushing, roll coating, spray coating, air spray, Methods such as airless spraying and divebing can be used. The coating thickness (after drying) is not particularly limited, and can be selected from a range of about 5 μΐη—50 mm (for example, 5 / im—10 mm) depending on the application. It is preferably about 30-3000 μm, more preferably about 50-1000 / im (particularly 100-500 μ μη). According to the present invention, even when the film is thickly applied, the generation of bubbles can be suppressed, and the decrease in the film thickness (thinning) due to drying can be suppressed. Therefore, it is useful for forming a coating film having a large film thickness and high surface smoothness.

[0076] The solvent-free composition of the present invention can be cured at room temperature or by heating (for example, heating at about 50 to 100 ° C) after being applied to a substrate to form a coating film. In the present invention, the composition can be rapidly cured even at room temperature (for example, about 15 to 25 ° C.). ADVANTAGE OF THE INVENTION The solvent-free composition of this invention can ensure sufficient pot life, and the drying or hardening time is short, and workability is high.

[0077] Since the solvent-free composition of the present invention is excellent in adhesion to a substrate and various coating properties, it can be used for coating and bonding various substrates. Examples of the substrate include a substrate made of an inorganic material such as metal, ceramics, glass, mortar, and concrete, and an organic material such as a synthetic resin or a natural material (such as wood). Special In addition, when the polyol component is composed of a low-molecular polyol, a smooth and strong coating film can be formed without being affected by the surface shape of the substrate having a high hardness, so that a substrate having a non-flat surface (for example, mortar, This is effective for porous substrates such as concrete and wood) and substrates having irregularities such as rough surfaces and steps. Further, when the polyol component is composed of a low molecular polyol and a polymer polyol, and the polymer polyol has an ultraviolet absorbing group, the coating film has excellent light resistance, and thus is suitable for outdoor use and the like.

Industrial applicability

[0078] The solvent-free composition of the present invention can be used for various purposes, for example, for surface finishing of buildings and structures, for surface finishing of machines and tools, and for the surface and various surfaces of piping such as sewers and gases. It can be used for interior surfaces, surface finishing of home appliances, furniture, daily necessities, etc., surface and interior surfaces of containers and containers, etc., and protective finish of various vehicle outer panel coating films. Among these applications, especially when the polyol component is composed of low-molecular-weight polyols, various types of buildings and structures (e.g., floors, walls, ceilings, sewer systems, roads, railways, airport runways, ports and harbors) Equipment, underwater equipment or their ancillary equipment, tunnel inner walls, etc.), especially useful for buildings and structures with a rough surface, and various products with uneven shapes such as steps, etc., made of cement, concrete, wood, etc. It is. Furthermore, when the polyol component is composed of a low molecular polyol and a polymer polyol, it is used for the surface finishing of textile products, etc., and for the colorful finishing of concrete floors mixed with coarse particles of various natural stones or artificially colored coarse particles. It is useful for heat insulation and heat-insulating finishing in which flakes such as urethane foam are blended, or for bonding these products or between these products and other products.

Example

[0079] Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

The contents of the components used in the examples and comparative examples, and methods for evaluating the properties of the compositions and coating films are shown below.

[0081] (1) Contents of each component

[Polyol component (A)]

Low molecular polyol A1-1: Diethylene glycol, reagent first class, purity 99% by weight or more Low molecular polyol Al-2: propylene glycol, manufactured by Showa Denko KK, industrial use, molecular weight 76.1, specific gravity (25.C) 1.038, viscosity (25.C) 43 mPa * s

Low molecular polyol A1-3: 1,4-butanediol, manufactured by Mitsubishi Chemical Corporation, molecular weight 90.1, specific gravity (25.C) 1.015, viscosity (25 ° C) 68 mPa-s

Low molecular weight polyol Al_4: l, 6-hexanediol, reagent primary, molecular weight 118, melting point 4 1-42 ° C

Low molecular polyol A1-5: Dipropylene glycol, manufactured by Kishida Chemical Co., Ltd., Reagent 1st grade, molecular weight 134.2, specific gravity (25 ° C) 1.025, viscosity (25.C) 73mPa's

Polymer polyol A2-1: Acrylic polyol, manufactured by Nippon Shokubai Co., Ltd., trade name "U Double H_4818", nonvolatile content 70% by weight, viscosity (25 ° C) Z-Z (Gardner) (4630-

9850cSt (46.3 98.5cm ² Zs)), hydroxyl value (value in varnish) 70K〇Hmg Solution containing xylene and butyl acetate

Polymer polyol A2 - 2: UV absorbing acrylic polyol, manufactured by Nippon Shokubai Co., Ltd., trade name "HALSHYBRID GP1034-3", nonvolatile content 40 weight ^_0/0, the viscosity (25 ° C) 80mPa • s , a hydroxyl value (Varnish) 36K〇Hmg / g, Ethyl acetate containing solution

Polymer polyol A2-3: Highly weather-resistant acrylic polyol, manufactured by Rohm & Haas Co., Ltd., trade name "Paraloid UCD_750", viscosity (25 ° C) 5000 mPa's, specific gravity (25 ° C) 1.04, hydroxyl equivalent (solid) 400, heating residue (% by weight) 80, n-butyl acetate-containing solution Polymer polyol A2-4: Polyester polyol, manufactured by Mitsui Takeda Chemiconore Co., Ltd., trade name “Takelac U118A”, nonvolatile content 97%, viscosity (25 ° C) 3500mPa's, specific gravity (25 ° C) 1.04, acid value 219

Polymer polyol A2-5: Polyester polyol, manufactured by Mitsui Takeda Chemiconore Co., Ltd., trade name “MT Forester C-1000”, 100% non-volatile, viscosity (25.C) UV (Gardner), hydroxyl value 161, iodine value 86 .

[Polyisocyanate component (B)]

Polyisocyanate B—1: Trade name “Takenate D_l 70N”, manufactured by Mitsui Takeda Chemical Co., Ltd., hexamethylene diisocyanate trimer, molecular weight 504, specific gravity (25 ° C) 1.16, viscosity (25 °) C) 2000mPa-s Polyisocyanate B-2: trade name "Coronate R301", manufactured by Nippon Polyurethane Industry Co., Ltd., viscosity (25 ° C) 800 mPa's

Polyisocyanate B-3: trade name "Coronate R303", manufactured by Nippon Polyurethane Industry Co., Ltd., viscosity (25 ° C) 200 mPa's

Aqueous polyisocyanate B—4: Trade name “Aquanate AQ—200”, manufactured by Nippon Polyurethane Industry Co., Ltd., viscosity (25 ° C) Y—Z (Gardner)

Polyisocyanate B-5: trade name "Takenate D-170HN", manufactured by Mitsui Takeda Chemical Co., Ltd., hexamethylene diisocyanate trimer, specific gravity (25 ° C) 1.14, viscosity (25 ° C) 600mPa • s

Polyisocyanate B-6: Trade name “Takenate D_l 77N”, manufactured by Mitsui Takeda Chemical Co., Ltd., hexamethylene diisocyanate trimer, specific gravity (25 ° C) 1.10, viscosity (25.C) 250 mPa -s ₀

[Epoxy Group-Containing Compound (C)]

Glycidyl ether C-1: neopentyl glycol diglycidyl ether, trade name "Denacol EX211", manufactured by Nagase ChemteX Corporation, molecular weight 216, epoxy equivalent 140g / eq, specific gravity 1.07, viscosity (25 ° C) 14mPa's

Glycidyl ether C-1 2: Hexamethylene glycol diglycidyl ether, trade name "Denacol EX212", manufactured by Nagase ChemteX Corporation, molecular weight 230, epoxy equivalent 150g / eq, specific gravity (25 ° C) 1.06, viscosity (25 °) C) 20mPa's

Glycidyl ether C-1-3: glycerol polyglycidyl ether, trade name "Denacol EX313", manufactured by Nagase ChemteX Corporation, epoxy equivalent 141g / eq, specific gravity (25 ° C) 1.22, viscosity (25.C) 150mPa- s

Glycidyl ether C-4: Trimethylolpropane polyglycidyl ether, trade name "Denacol EX321", manufactured by Nagase ChemteX Corporation, epoxy equivalent 140 g / eq, specific gravity (25.C) 1.15, viscosity (25 ° C) 130 mPa -s.

[0084] [Other additives]

DBTDL: dibutyltin dilaurate, trade name "L101_V", manufactured by Tokyo Fine Chemical Canole Co., Ltd., 2% by weight xylene solution and 3% by weight xylene solution Titanium white A: Trade name "JR901", manufactured by Tika Corporation

Titanium white B: trade name "JR701", manufactured by Tika Corporation

Stainless flakes: trade name "RFA4000", manufactured by Toyo Aluminum Co., Ltd.

Zinc powder: trade name "#F", manufactured by Sakai Danigaku Kogyo Co., Ltd.

Aluminum paste: Product name "1900M", manufactured by Toyo Aluminum Co., Ltd.

Talc: Trade name "Talc P", manufactured by Fuji Talc

My power: WG My power 325 (trade name), manufactured by Shiraishi Industry Co., Ltd.

Colloidal light calcium carbonate: trade name "MC_K", manufactured by Maruo Calcium Co., Ltd. Dispersant: trade name "antigel", manufactured by Schwecman

Thixotropy-imparting agent: Trade name "DISPARON A603-20X", manufactured by Kusumoto Kasei Co., Ltd. Defoamer A: trade name "BYK066", manufactured by Schwecman

Defoamer B: Trade name "Mitsutel S", manufactured by Schwecman

Silane coupling agent: γ-glycidoxypropyltrimethoxysilane, trade name “NUCA187”, manufactured by Nippon Tunicer Co., Ltd., specific gravity (25 ° C) 1.07, boiling point 290. C, flash point 135 ° C.

[0085] (2) Evaluation method of each characteristic

The obtained coating composition is lightly polished with sandpaper # 240, and tinplate described in JIS_K_54102 (3), tinplate washed with toluene, SPTE 1505003), and painted on one side with a brush. After curing for 5 days (5 days for Examples 19 to 23 and Comparative Examples 8 to 18), the coated articles were subjected to the following property evaluation tests. In the case of the water resistance, acid resistance and alkali resistance tests, the unpainted surfaces were all sealed with a commercially available electric insulating tape (black) and then subjected to each test.

[0086] [VOC]

It was determined by calculation from the composition of the blended components.

[0087] [Viscosity]

Measured at a temperature of 25 ° C using a B-type viscometer

[Workability]

After preparing the coating film, the time during which coating was possible was measured and evaluated according to the following criteria.

[0088] ©: 5 8 hours 〇: 3 hours or more and less than 5 hours

△: 1 hour or more and less than 3 hours

X: less than l hours.

[Dryability of coating film]

According to JIS-K-5400 6.5, evaluation was made according to the following criteria.

[0090] ©: Dried within 8 hours

〇: More than 8 hours, dried within 24 hours

Δ: Dried within 48 hours over 24 hours

X: dried after more than 48 hours.

[0091] [Available time]

In Examples 19 to 23 and Comparative Examples 818, after the urethane-based resin composition was prepared, the time during which coating was possible at 25 ° C. was measured.

[0092] [Brushing workability]

In Examples 19 to 23 and Comparative Examples 8 to 18, the obtained urethane-based resin compositions were applied to one surface of a flexible asbestos board (70 mm long × 150 mm wide × 3 mm thick) in each of the vertical and horizontal directions. The brush was alternately returned five times and painted, and the degree of difficulty of brush separation was evaluated according to the following criteria.

[0093] A: Good

〇: Slightly heavy

△: Very heavy.

[0094] [Drying time]

For Examples 19 to 23 and Comparative Examples 818, the drying time at 25 ° C. was measured according to JIS_K_54006.5, and evaluated according to the following criteria.

[0095] ©: Dry in less than 5 hours

〇: Dry for more than 5 hours and less than 12 hours

△: Dry for 12 hours or more and less than 24 hours

X: Dry for more than 24 hours.

[0096] [Appearance of coating film] According to JIS-K-5400 7.1, transparency and gloss were evaluated according to the following criteria. Regarding the generation of bubbles, the film thickness was measured at a portion where two or more bubbles were observed on the coated surface, and evaluated according to the following criteria. In Experimental Examples 2 and 3, the gloss was measured at an incident angle of 60 ° according to JIS-K-5400 7-6.

[0097] (Transparency)

◎: almost colorless and transparent

〇: translucent

△: cloudy

(Glossy)

◎: Good

〇: Semi-gloss

△: 3 minutes or less

(Degree of foam generation)

◎: 200 μΐη or more

0: 100 μm or more and less than 200 μm

Α: 50 βm or more and less than 100 μm

X: less than 50 μm.

[0098] [State of coating film]

With respect to Examples 19 to 23 and Comparative Examples 8 to 18, the gloss, sharpness, and leveling of the dried coating film were visually observed and evaluated according to the following criteria.

[0099] ◎: High gloss, sharpness, and leveling

〇: Gloss, sharpness and leveling are normal

X: Low gloss, sharpness, and leveling.

[0100] [Thickness]

The film thickness was measured at five locations using a micrometer, and the average value was determined.

[0101] [Pencil hardness]

Measured according to JIS-K-5400 8.4.2.

[0102] [Bending resistance] A mandrel having a diameter of 6 mm (diameter 3 mm for Examples 19 to 23 and Comparative Examples 8 to 18) was used. The evaluation was performed according to the following criteria according to JIS_K_54008.1.

[0103] ◎: No abnormality

〇： Shallow crack occurred

X: Peeling.

[0104] [Adhesiveness]

A cross-cut test was performed in accordance with JIS-K-5400 8.5.2. The larger the value, the stronger the adhesion. In Examples 19 to 23 and Comparative Examples 8 to 18, a cross-cut test was performed in the same manner, and evaluated according to the following criteria.

[0105] :: Peeling of coating film is less than 10%

〇: Peeling of coating film is 10% or more and less than 50%

△: 50% or more and less than 90% of peeling of the coating film

X: The peeling of the coating film is 90% or more.

[0106] [Water resistance]

After dipping the coating film in water at 20 ° C for 7 days, the state of the coating film surface was visually observed and evaluated according to the following criteria. In Experimental Examples 2 to 4, evaluation was performed after immersion for 30 days. In Examples 19 to 23 and Comparative Examples 8 to 18, evaluation was performed after immersion for 10 days.

[0107] A: No change in coating film surface

〇: Slight swelling on the coating surface

X: Most of the coating film surface is eluted or peeled.

[0108] [Salt water resistance]

After immersing the coating film in 3% by weight saline for 30 days, the state of the coating film surface was visually observed and evaluated according to the following criteria.

[0109] ◎: No change in coating film surface

〇: Slight swelling on the coating surface

X: It occurs on most of the coating film surface.

[0110] [Acid resistance]

After immersing in 10% by weight sulfuric acid at room temperature for 10 days, visually observe the state of the coating film surface, Evaluation was made according to the following criteria.

[0111] A: No change in coating film surface

〇: Slight swelling on the coating surface

X: Swelling or 鲭 generation on most of the coating film surface.

[0112] [Alkali resistance]

After immersion in saturated lime water at room temperature for 10 days, the state of the coating film surface was visually observed and evaluated according to the following criteria.

[0113] ◎: No change on the coating film surface

〇: Slight swelling on the coating surface

X: Swelling occurred on most of the coating film surface.

[0114] [Alcohol resistance]

After immersion in isopropyl alcohol at room temperature for 10 days, the state of the coating film surface was visually observed and evaluated according to the following criteria.

[0115] :: No change in coating film surface

〇: The coating surface slightly swells

X: Swelling occurred on most of the coating film surface.

[0116] [Volatile oil resistance]

In accordance with JIS-K-5400 8.24, after immersion in test volatile oil No. 1 for 10 days, the state of the coating film surface was visually observed and evaluated according to the following criteria.

[0117] ◎: No change on the coating film surface

〇: Slight swelling on the coating surface

Δ: Swelling occurred on most of the coating film surface

X: The coating film was completely peeled.

[0118] [Boiling water resistance]

After immersion in boiling water for 5 hours, the state of the coating film surface was visually observed and evaluated according to the following criteria.

[0119] :: No change in coating film surface

〇: Slight swelling on the coating surface X: Most of the coating surface peeled off.

[0120] [Accelerated exposure test]

After irradiation for 500 hours with a due cycle type weatherometer, the state of the coating film was visually observed and evaluated according to the following criteria.

[0121] A: almost no change in coating film

〇: The coating film is slightly discolored and the gloss is slightly reduced

X: The coating film is considerably discolored.

[0122] [Cleaning property]

Put a mark of 〇 on the surface of the coating film with a commercially available oil-based magic pen (black), and after 30 minutes (24 hours for Examples 19 to 23 and Comparative Examples 8 to 18), Kimwipe S200 ( (Manufactured by Crecia Corporation) and the degree of cleaning was evaluated according to the following criteria.

[0123] ◎: △ mark completely disappeared

〇: Most of the 〇 mark disappeared

△: A small part of the △ mark disappeared

X: 〇 mark does not disappear.

[0124] [Heat resistance]

After heating at 150 ° C for 3 hours, the appearance and adhesion of the coating film were tested. The appearance of the coating film was evaluated according to the following criteria, and the adhesion was evaluated by the above method.

[0125] A: Almost no change in coating film

〇: Slight discoloration of coating film

Δ: The coating film was considerably yellowed.

[0126] [Light resistance]

The obtained urethane-based resin composition is applied once on a single surface of a polycarbonate plate (80 mm long × 150 mm wide × 2 mm thick) with a brush, cured in a room (room temperature) for 5 days, and then measures 33 mm long × 45 mm wide. After irradiating with a UV irradiator (trade name "Super UV Tester SUV-F11, Iwasaki Electric Co., Ltd.") for 48 hours, the degree of change in the appearance of the coating film was visually compared with that before irradiation. The evaluation was performed according to the following criteria.

[0127] ◎: Very slight discoloration 〇: There was considerable discoloration

Δ: Discoloration was remarkable.

[Coatability on Styrofoam]

The obtained urethane-based resin composition was applied once with a brush on one side of a styrene foam plate (length 100 mm × width 100 mm × thickness 30 mm), and the finished state was visually observed and evaluated according to the following criteria.

[0129] A: Film formation was possible without dissolving the ground

〇: Some of the ground was melted, but film formation was possible

X: The base was dissolved.

[0130] Example 1

In a plastic beaker, add 204 parts by weight of glycidyl ether C-2, 7 parts by weight of DBTDL (2% by weight solution), and 94 parts by weight of polyol A1-1, and uniformly stir using a table stirrer. A preparation was prepared. To this A agent, 702 parts by weight of polyisocyanate B-1 was added as B-IJ, and the mixture was further uniformly stirred to obtain a desired composition. Table 1 shows the composition of this composition, and Table 2 shows the results of evaluating various properties.

[0131] Example 2

In a plastic beaker, add 135 parts by weight of glycidyl ether C_2, 8 parts by weight of DBTDL (3% by weight solution), and 45 parts by weight of polyol A1-2, and uniformly stir using a tabletop stirrer. An agent was prepared. To this A agent, 820 parts by weight of an aqueous polyisocyanate B-4 was added as a B IJ, and the mixture was further uniformly stirred to obtain a desired composition. Table 1 shows the composition of this composition, and Table 2 shows the results of evaluating various properties.

[0132] Example 3

In a plastic beaker, add 208 parts by weight of glycidyl ether C-2, 7 parts by weight of DBTDL (2% by weight solution), 17 parts by weight of polyol A1-2, and 61 parts by weight of polyol A1-3. The mixture was stirred uniformly using to prepare Agent A. To this A agent, 714 parts by weight of polyisocyanate B-1 as an B agent was added, and the mixture was further uniformly stirred to obtain a desired composition. Table 1 shows the composition of this composition, and Table 2 shows the results of evaluating various properties. [0133] Example 4

A composition was obtained according to Example 3, except that the proportions were as shown in Table 1. Table 1 shows the composition of this composition, and Table 2 shows the results of evaluating various properties.

Example 5—12

A composition was obtained according to Example 13 except that the components shown in Table 1 were used. Table 1 shows the composition of these compositions, and Table 2 shows the results of evaluating various properties.

Example 13

In a plastic beaker, add 202 parts by weight of glycidyl ether C-1 and 104 parts by weight of polyol A1-4, dissolve them by heating to about 60 ° C, and add 08 parts (2% by weight solution). A quantity was reduced, and the mixture was uniformly stirred using a table stirrer to prepare Agent A. To this A agent, 694 parts by weight of polyisocyanate B-1 was added as an B agent, and the mixture was further uniformly stirred to obtain a target composition. Table 1 shows the composition of this composition, and Table 2 shows the results of evaluating various properties.

[0136] Example 14

To Agent A prepared according to Example 4, 6 parts by weight of dispersant, 4 parts by weight of thixotropic agent, 5 parts by weight of defoamer AO, 5 parts by weight of defoamer B, 0.5 parts by weight of titanium white A408 parts by weight The mixture was mixed with a glass rod and kneaded twice using a small three-roll mill to obtain Agent A. To this A agent, 716 parts by weight of polyisocyanate B-1 as an B agent was added, and the mixture was further uniformly stirred to obtain a desired composition. Table 1 shows the composition of this composition, and Table 2 shows the results of evaluating various properties.

[0137] Example 15

To Agent A prepared according to Example 4, further added 4 parts by weight of a thixotropy-imparting agent, 5 parts by weight of an antifoaming agent AO, 5 parts by weight of an antifoaming agent IjBO.5 parts by weight, and 130 parts by weight of stainless flakes. Using a table stirrer, the mixture was stirred uniformly to obtain Agent A. To this A agent, 716 parts by weight of a polyisocyanate B-1 was added as an B agent, and the mixture was further uniformly stirred to obtain a desired composition. Table 1 shows the composition of this composition, and Table 2 shows the results of evaluating various properties. Example 16

Except for using the components shown in Table 1, the agent A prepared according to Examples 13 to 13 was further added with 15 parts by weight of a titatropic enhancer, 5 parts by weight of an antifoaming agent AO, and 5 parts by weight of an antifoaming agent BO. Then, the mixture was stirred uniformly using a table stirrer to obtain Agent A. To this A agent, add 680 parts by weight of polyisocyanate B-2 as the B agent, stir uniformly, and then add 3000 parts by weight of zinc dust as the C agent, stir uniformly, and stir uniformly. A composition was obtained. Table 1 shows the composition of this composition, and Table 2 shows the results of evaluating various properties.

Example 17

Except for using the components shown in Table 1, the agent A prepared in accordance with Example 13 was further added with 4 parts by weight of a dispersant, 5 parts by weight of a thixotropic agent, 5 parts by weight of an antifoaming agent AO. Add 0.5 parts by weight of Agent B, 100 parts by weight of titanium white B, 170 parts by weight of talc, and 130 parts by weight of my strength, premix with a glass rod, and knead it twice using a small three-roller. Agent was obtained. To this A agent, 680 parts by weight of polyisocyanate B-2 was added as the B agent, and the mixture was stirred uniformly. Then, as the C agent, 136 parts by weight of the aluminum paste was added, and the mixture was stirred uniformly. The composition was obtained. Table 1 shows the composition of this composition, and Table 2 shows the results of evaluating various properties.

[0140] Example 18

Except for using the components shown in Table 1, the agent A prepared according to Examples 13 to 13 was further added with an antifoaming agent AO.5 parts by weight, an antifoaming agent B0.5 parts by weight, titanium white B45 parts by weight, colloid 370 parts by weight of light carbon dioxide was added, mixed in advance with a glass rod, and then kneaded once using a small three-roll mill to obtain Agent A. To this A agent, 554 parts by weight of polyisocyanate B-1 was added as an B agent, and the mixture was stirred uniformly to obtain a target composition. Table 1 shows the composition of this composition, and Table 2 shows the results of evaluating various properties.

[0141] [Table 1] table 1

Table 2

As is evident from the results in Table 2, the compositions of Examples have good coating properties such as drying property, coating state, hardness, adhesion, bending resistance, water resistance and cleaning property.

[0143] Comparative Example 1

In a plastic beaker, 460 parts by weight of glycidyl ether C-1 and 7 parts by weight of DBTDL (2% by weight solution) were added, and the mixture was stirred uniformly using a table stirrer to prepare the agent A. As B, 540 parts by weight of polyisocyanate B-1 was added, and the mixture was stirred uniformly again to obtain a desired composition. Table 3 shows the results of evaluating various properties of this composition.

[0144] Comparative Example 2-5

A composition was obtained according to Comparative Example 1, except that the components shown in Table 3 were used. Table 3 shows the results of evaluating various properties of this composition.

[0145] Comparative Example 6

In a plastic beaker, add 187 parts by weight of glycidyl ether C_3, 185 parts by weight of glycidyl ether C-14, and 7 parts by weight of 08 (2% by weight solution) and uniformly stir using a table stirrer. Thus, Agent A was prepared, and then, as Agent B, 628 parts by weight of polyisocyanate B-2 was added, and the mixture was stirred uniformly again to obtain a target composition. Table 3 shows the results of evaluating various properties of this composition.

[0146] Comparative Example 7

A composition was obtained according to Comparative Example 6, except that the components shown in Table 3 were used. Table 3 shows the results of evaluating various properties of this composition.

[Table 3]

As is evident from the results in Table 3, the composition of the comparative example had low properties such as drying property, coating film state, hardness, and adhesion.

Experimental example 1

After the composition obtained in Example 11 was aged in a room for 30 minutes, an A4 size (thickness: lmm) polycarbonate resin plate (Panlite sheet PC1151, manufactured by Teijin Chemicals Ltd.) was coated on one side with a bar coater ( (36 xm) once to prepare Test Specimen 1. The sex was evaluated. Table 4 shows the evaluation results.

[0149] [Table 4]

Table 4

As is clear from the results in Table 4, the composition of Example 11 has high coating film properties. Therefore, it is suitable for application as a coating agent to a polycarbonate plate, an acrylic plate (polymethyl methacrylate plate), a polystyrene plate, and the like, which are regarded as weak solvent plastics.

[0150] Experimental example 2

Using the compositions obtained in Examples 14, 16, and 17, the following test pieces 2 and 3 were produced, and the characteristics were evaluated. Table 5 shows the properties of these compositions.

[0151] Specimen 2: The composition obtained in Example 16 was entirely polished with sandpaper # 240 and completely washed with toluene and washed with a steel sheet (a steel sheet described in JIS-5141, SPCC1507008). The composition was applied once with a brush, and the composition obtained in Example 14 was further applied to the entire surface twice with a brush.

Test piece 3: The composition obtained in Example 17 was applied twice with a brush to the entire surface of a steel sheet treated in the same manner as Test piece 2, and the composition obtained in Example 14 was further applied with a brush. Two times, a total of four coats were prepared.

[0153] Each of the test pieces 2 and 3 was cured in a room for 7 days before being subjected to each property test.

[0154] [Table 5] Table 5

As is clear from the results in Table 5, the test pieces coated with the compositions obtained in Examples 14, 16 and 17 have performance enough to withstand practical use in a general environment.

[0155] Experimental example 3

The composition obtained in Example 14 was coated twice with a brush on one side of a flexible asbestos sheet 1 SK-5410 2- (6) whose surface was cleaned with Kimwipe S200 (manufactured by Crecia Co., Ltd.). Piece 4 was prepared, cured for 7 days in a room, and then evaluated for properties. Table 6 shows the results.

[0156] [Table 6]

Table 6

As is clear from the results in Table 6, the composition obtained in Example 14 is excellent in various resistances Therefore, it is suitable as a coating agent for the purpose of cosmetic and protection of cement materials.

[0157] Experimental example 4

On one side of the flexible asbestos board used in Experimental Example 3, apply the composition obtained in Example 18 and place a mold so as to have a thickness of 2 mm, apply a plastic spatula, and remove the mold. After the removal, the sample was fixed at an angle of 60 ° and dried in a room to prepare a test piece 5. After curing in a room for 7 days, the properties of the coating film were evaluated. Table 7 shows the results.

[Table 7]

Table 7

As is clear from the results in Table 7, the composition obtained in Example 18 can be used as a thick coating agent and a sealing agent for joints.

Example 19

In a container, 67 parts by weight of low-molecular polyol A1-5, 433 parts by weight of polymer polyol A2-1 (303 parts by weight of solid content), 151 parts by weight of glycidinoleether C-12, and DBTDL (2% by weight) Add 6.5 parts by weight of xylene solution), stir evenly using a table stirrer, and remove the solvent in the polymer polyol A2-1 at a temperature of 80 ° C and a pressure of 6-20 mmHg. Thus, Agent A was prepared. The solid concentration of Agent A before the solvent exchange was 46.1% by weight, and the solid concentration of Agent A after the solvent exchange was 58.1% by weight. The viscosity of the A agent was 5000 mPa's at a temperature of 25 ° C, and the composition thereof was calculated as follows: 100 parts by weight of the polymer polyol A2_l and 22 parts of the low molecular weight polyol A1-5 in terms of solid content. About 50 parts by weight of glycidyl ether.

[0160] Next, 172 parts by weight of the agent A, 166 parts by weight of the polyisocyanate B-1 as "B-I" were added, and the mixture was further uniformly stirred to obtain a desired urethane-based resin composition. Was. The miscibility of the A agent and the B agent was good, and the viscosity immediately after mixing was 3050 mPa's at a temperature of 25 ° C. This ゥ Table 8 shows the composition (solid content) of the urethane resin composition, and Table 8 shows the results of evaluating various properties.

[0161] Example 20

In a container, 38 parts by weight of low molecular weight polyol A1-2, 350 parts by weight of polymer polyol A2-2 (140 parts by weight of solid content), 75.5 parts by weight of glycidinoleether C-12, Add 3 parts by weight of DBTD (2% by weight xylene solution) and uniformly stir using a tabletop stirrer. Then, at a temperature of 80 ° C and a pressure of 6 lOmmHg, polymer polymer A2- Agent A was prepared by removing the solvent in 2. Before the solvent exchange, the solid content concentration of the agent A was 30% by weight, and after the solvent exchange, the solid concentration of the agent A was 55.2% by weight. The viscosity of Agent A is 6500 mPa's at a temperature of 25 ° C. The composition is 27 parts by weight of low-molecular-weight polyol A1-2 with respect to 100 parts by weight of polymer polyol A2-2 in terms of solid content. Parts by weight, and glycidyl ether C-2 was about 54 parts by weight.

[0162] Next, 160 parts by weight of polyisocyanate B-5 was added as B-IJ to 181 parts by weight of Agent A, and the mixture was further uniformly stirred to obtain a target urethane-based resin composition. The miscibility between Part A and Part B was somewhat difficult, and the viscosity immediately after mixing was 3200 mPa's at a temperature of 25 ° C. Table 8 shows the composition (solid content) of the urethane-based resin composition, and Table 8 shows the results of evaluating various characteristics.

[0163] Example 21

In a container, 11 parts by weight of low molecular polyol A1-3, 125 parts by weight of polymer polyol A2-3 (100 parts by weight of solid content), 18 parts by weight of glycidinoleether C-2, and DBTDL (2% by weight) Xylene solution) was added to 1 part by weight, and the mixture was uniformly stirred using a tabletop stirrer to prepare Agent A. To this A agent, 143 parts by weight of polyisocyanate B-1 was added as B mixture, and the mixture was stirred uniformly to obtain a target urethane resin composition. The miscibility of Agent A and Agent B was good, and the viscosity immediately after mixing was 1200 mPa's at a temperature of 25 ° C. Table 8 shows the composition (solid content) of the urethane-based resin composition, and Table 8 shows the results of evaluating various characteristics.

[0164] Example 22

In a container, 38 parts by weight of low-molecular-weight polyol A1-2 and 1000 parts of polymer polyol A2-4 A part A was prepared by adding 2 parts by weight of 08 parts (2 parts by weight of xylene solution) and stirring uniformly using a tabletop stirrer. To this agent A, 284 parts by weight of polyisocyanate B-1 was added as B IJ, followed by uniform stirring to obtain a desired urethane-based resin composition. The miscibility of Agent A and Agent B was good, and the viscosity immediately after mixing was 1150 mPa's at a temperature of 25 ° C. Table 8 shows the composition (solid content) of the urethane-based resin composition, and Table 8 shows the results of evaluating various properties.

Example 23

In a container, 11 parts by weight of low-molecular-weight polyol A1-2, 100 parts by weight of polymer polyol A2-4, 58 parts by weight of glycidyl ether C-2, and 1380 parts (2% by weight xylene solution) are 2 parts by weight. In addition, Part A was prepared by uniformly stirring using a table stirrer. To this A agent, 437 parts by weight of polyisocyanate B-1 was added as an B agent, and the mixture was stirred uniformly to obtain a desired urethane resin composition. The miscibility of the A agent and the B agent was good, and the viscosity immediately after mixing was 750 mPa's at a temperature of 25 ° C. Table 8 shows the composition (solid content) of the urethane-based resin composition, and Table 8 shows the results of evaluating various characteristics.

[0166] Comparative Example 8

To a container, add 142.9 parts by weight of polymer polyol A2-1 (100 parts by weight of solid content), and 1 part by weight of 08 (2% by weight xylene solution), and mix uniformly using a table stirrer. Agent A was prepared by stirring. To this A agent, 36 parts by weight of polyisocyanate B-6 as an B agent was added, followed by stirring to obtain a target urethane resin composition. The miscibility between the A agent and the B agent was good, and the viscosity immediately after mixing was 2150 mPa's at a temperature of 25 ° C. Table 8 shows the composition (solid content) of the urethane-based resin composition, and Table 8 shows the results of evaluating various characteristics.

[0167] Comparative Example 9

Add 250 parts by weight of polymer polyol A2-2 (100 parts by weight of solid content) and 1 part by weight of DB (2% by weight xylene solution) to a container and stir uniformly using a table stirrer. Was used to prepare Agent A. 33 parts by weight of polyisocyanate B-5 was added to Agent A as Agent B, followed by stirring to obtain a target urethane resin composition. Agent A and Agent B Had good miscibility, and the viscosity immediately after mixing was 100 mPa's at a temperature of 25 ° C. Table 8 shows the composition (solid content) of the urethane-based resin composition, and Table 8 shows the results of evaluating various characteristics.

[0168] Comparative Example 10

To a container, add 125 parts by weight of polymer polyol A2-3 (100 parts by weight of solid content) and 2 parts by weight of DB (2% by weight xylene solution) and stir uniformly using a table stirrer. Was used to prepare Agent A. To this A agent, 52 parts by weight of polyisocyanate B-6 was added as an B agent, followed by stirring to obtain a desired urethane resin composition. The miscibility between the A agent and the B agent was good, and the viscosity immediately after mixing was 2800 mPa's at a temperature of 25 ° C. Table 8 shows the composition (solid content) of the urethane-based resin composition, and Table 8 shows the results of evaluating various characteristics.

[0169] Comparative Example 11

In a container, add 125 parts by weight of polymer polyol A2-3 (100 parts by weight of solid content), 30 parts by weight of silane coupling agent, and 2 parts by weight of 1 ^ (2% by weight xylene solution), and Agent A was prepared by uniformly stirring using a stirrer. To this A agent, 173 parts by weight of polyisocyanate B-1 as an B agent was added, followed by stirring to obtain a desired urethane resin composition. The miscibility of the A agent and the B agent was good, and the viscosity immediately after mixing was 3100 mPa's at a temperature of 25 ° C. Table 8 shows the composition (solid content) of this urethane-based resin composition, and Table 8 shows the results of evaluating various characteristics.

[0170] Comparative Example 12

100 parts by weight of polymer polyol A2-4 and 2 parts by weight of DBTDL (2% by weight xylene solution) were added to a container, and the mixture was uniformly stirred using a tabletop stirrer to prepare agent A. . To this A agent, 77 parts by weight of polyisocyanate B-1 was added as an B agent, followed by stirring to obtain a target urethane resin composition. The miscibility of the A agent and the B agent was good, and the viscosity immediately after mixing was 2875 mPa's at a temperature of 25 ° C. Table 8 shows the composition (solid content) of this urethane-based resin composition, and Table 8 shows the results of evaluating various properties.

[0171] Comparative Example 13 100 parts by weight of polymer polyol A2_4 and 2 parts by weight of DBTDL (2% by weight xylene solution) were added to a container, and the mixture was uniformly stirred using a table stirrer to prepare Agent A. To this A agent, 92 parts by weight of polyisocyanate B-1 was added as an B agent, followed by stirring to obtain a target urethane resin composition. The miscibility of the A agent and the B agent was good, and the viscosity immediately after mixing was 2525 mPa's at a temperature of 25 ° C. Table 8 shows the composition (solid content) of this urethane-based resin composition, and Table 8 shows the results of evaluating various properties.

[0172] Comparative Example 14

Add 100 parts by weight of Polymer Polyol A2-4 and 2 parts by weight of 08 (2% by weight xylene solution) to a container, and stir uniformly using a table stirrer to prepare Agent A. did. To this A agent, 82 parts by weight of polyisocyanate B-6 was added as an B agent, followed by stirring to obtain a desired urethane resin composition. The miscibility of the A agent and the B agent was good, and the viscosity immediately after mixing was 2200 mPa's at a temperature of 25 ° C. Table 8 shows the composition (solid content) of this urethane-based resin composition, and Table 8 shows the results of evaluating various properties.

[0173] Comparative Example 15

100 parts by weight of polymer polyol A2-4 and 2 parts by weight of DBTDL (2% by weight xylene solution) were added to a container, and the mixture was uniformly stirred using a table stirrer to prepare Agent A. . To this A agent, 98 parts by weight of polyisocyanate B-6 was added as an B agent, followed by stirring to obtain a target urethane resin composition. The miscibility of Agent A and Agent B was good, and the viscosity immediately after mixing was 2000 mPa's at a temperature of 25 ° C. Table 8 shows the composition (solid content) of this urethane-based resin composition, and Table 8 shows the results of evaluating various properties.

[0174] Comparative Example 16

Add 100 parts by weight of Polymer Polyol A2-5 and 3 parts by weight of 08 (2% by weight xylene solution) to a container and uniformly stir using a table stirrer to prepare Agent A. did. To this A agent, 58 parts by weight of polyisocyanate B-1 was added as an B agent, followed by stirring to obtain a target urethane resin composition. The miscibility of Agent A and Agent B is good, The viscosity immediately after mixing was 1300 mPa's at a temperature of 25 ° C. Table 8 shows the composition (solid content) of this urethane-based resin composition, and Table 8 shows the results of evaluating various properties.

[0175] Comparative Example 17

Add 100 parts by weight of Polymer Polyol A2-5 and 3 parts by weight of 08 (2% by weight xylene solution) to a container and uniformly stir using a table stirrer to prepare Agent A. did. To Part A, 60 parts by weight of polyisocyanate B-6 was added as Part B, followed by stirring to obtain a target urethane resin composition. The miscibility of Agent A and Agent B was good, and the viscosity immediately after mixing was 575 mPa's at a temperature of 25 ° C. Table 8 shows the composition (solid content) of the urethane-based resin composition, and Table 8 shows the results of evaluating various properties.

[0176] Comparative Example 18

60 parts by weight of polymer polyol A2-4, 40 parts by weight of polymer polyol A2-5, and 3 parts by weight of 08/100 (2% by weight xylene solution) are added to a container, and the mixture is uniformly mixed using a table stirrer. Agent A was prepared by stirring. To this agent A, 71 parts by weight of polyisocyanate B-1 as B IJ were added, followed by stirring to obtain a desired urethane resin composition. The miscibility of the A agent and the B agent was good, and the viscosity immediately after mixing was 2250 mPa • s at a temperature of 25 ° C. Table 8 shows the composition (solid content) of this urethane-based resin composition, and Table 8 shows the results of evaluating various properties.

[0177] [Table 8]

As is evident from the results in Table 8, the urethane-based resin compositions of the examples have good workability and coating film properties. On the other hand, in the urethane resin composition of the comparative example, any of the properties such as workability, coating film properties, and various resistances is not sufficient.

Claims

The scope of the claims

[I] A composition comprising a polyol component (A) and a polyisocyanate component (B), wherein the polyol component (A) comprises a low molecular weight polyol (A1) having a power of at least 350 or less. Solvent-free composition.

[2] The composition according to claim 1, wherein the viscosity of the low-molecular polyol (A1) is not more than 500 mPa's at 25 ° C.

[3] The polyisocyanate component (B) has a molecular weight of 150 to 3000, and the polyisocyanate component (B) has a molecular weight larger than that of the low-molecular polyol (A1). Composition.

[4] The composition according to claim 1, comprising a polyol component (A), a low molecular polyol (A1) as a diluent, and a polymer polyol (A2).

[5] Percentage power of low molecular polyol (A1) For 100 parts by weight of polymer polyol (A2),

5. The composition according to claim 4, wherein the composition is 5 to 100 parts by weight.

[6] The composition according to claim 4, wherein the composition is at least one selected from a polymer polyol (A2), a polyether polyol, a polyester polyol, a polycarbonate polyol and an acrylic polymer polyol.

[7] The composition according to claim 1, wherein the polyisocyanate component (B) is a derivative or a modified product of the polyisocyanate.

[8] The composition according to claim 1, wherein the molar ratio of the isocyanate group of the polyisocyanate component (B) is 0.5 to 1.5 mol per mol of the hydroxyl group of the polyol component (A). .

[9] The composition according to claim 1, further comprising a compound (C) having an epoxy group.

[10] The composition according to claim 9, wherein the compound (C) having an epoxy group is a compound having a viscosity at 25 ° C of 200 mPa · s and having a plurality of glycidinole groups.

[II] The composition according to claim 9, wherein the compound (C) having an epoxy group has a hydroxyl group.

[12] The set according to claim 9, wherein the proportion of the compound (C) having an epoxy group is 1 to 100 parts by weight based on 100 parts by weight of the total of the polyol component (A) and the polyisocyanate component (B). Adult.

[13] Diisocyanate polymer, C alkylene glycol, and aliphatic diol jig

2-6

A composition composed of ricidyl ether, wherein the isocyanate group of the multimer is 0.7 to 1.3 mol per 1 mol of the hydroxyl group of the alkylene glycol. A solvent-free composition having a ratio of 5 to 80 parts by weight based on 100 parts by weight of the total of the polymer and the alkylene glycol.

[14] Polio composed of C alkylene glycol and acrylic polymer polyol

2-6 A composition comprising an alcohol component, a diisocyanate multimer, and a diglycidyl ether of an aliphatic diol, wherein the ratio of isocyanate groups in the diisocyanate multimer is based on 1 mole of hydroxyl groups in the polyol component. , 0.71.3 monole

2-6 Proportion of render recall A solventless composition that is 780 parts by weight based on ₁₀₀ parts by weight of an acrylic polymer polyol.

[15] The composition according to claim 1, which is a coating agent or an adhesive.

[16] A method for coating a surface of a substrate with the composition according to claim 1 to form a coating film.

17. The method according to claim 16, wherein the substrate has a non-flat surface.